Substituted aromatic thiocarboxylic acid amides and their use as herbicides

ABSTRACT

Disclosed are substituted aromatic thiocarboxamide compounds of the formula:                    
     their use as herbicides and the process of making said compounds.

This application is a divisional of application Ser. No. 09/470,583,filed on Dec. 22, 1999 now U.S. Pat. No. 6,331,507, which is adivisional of application Ser. No. 08/732,257, filed on Oct. 28, 1996,now U.S. Pat. No. 6,077,813, issued Jun. 20, 2000, which is a 371 ofPCT/EP 95/01507, filed Apr. 21, 1995.

The invention relates to novel substituted aromatic thiocarboxamides, toprocesses for their preparation and to their use as herbicides.

It is already known that certain aromatic carbothioamides, for example2,6-dichloro-benzothioamide (“chlorthiamid”), possess herbicidalproperties (cf. GB-B 987253). However, the activity of this previouslyknown compound, especially at low application rates and concentrations,is not entirely satisfactory in all areas of application.

The novel substituted aromatic thiocarboxamides have now been found ofthe general formula (I)

in which

R¹ represents hydrogen or halogen,

R² represents the following group

—A¹—A²—A³

 in which

A¹ represents a single bond, or represents oxygen, sulphur, —SO—, —SO₂—,—CO— or the group —N—A⁴—, in which A⁴ represents hydrogen, hydroxyl,alkyl, alkenyl, alkinyl, alkoxy, aryl, alkylsulphonyl or arylsulphonyl,

A¹ additionally represents in each case optionally substitutedalkanediyl, alkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl orarenediyl,

A² represents a single bond, or represents oxygen, sulphur, —SO—, —SO₂—,—CO— or the group —N—A⁴—, in which A⁴ represents hydrogen, hydroxyl,alkyl, alkenyl, alkinyl, aryl, alkoxy, alkylsulphonyl or arylsulphonyl,

A² additionally represents in each case optionally substitutedalkanediyl, alkenediyl, alkinediyl, cycloalkanediyl, cycloalkenediyl orarenediyl,

A³ represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato,nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl,halogen or represents in each case optionally substituted alkyl, alkoxy,alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino,alkoxycarbonyl, dialkoxy(thio)phosphoryl, alkenyl, alkenyloxy,alkenylamino, alkylideneamino, alkenyloxycarbonyl, alkinyl, alkinyloxy,alkinylamino, alkinyloxycarbonyl, cycloalkyl, cycloalkyloxy,cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino,cycloalkyloxycarbonyl, cycloalkylalkoxycarbonyl, aryl, aryloxy,arylalkyl, arylalkoxy, aryloxycarbonyl, arylalkoxycarbonyl,heterocyclyl, heterocyclylalkyl, heterocyclylalkoxy orheterocyclylalkoxycarbonyl,

R³ represents hydrogen or halogen or together with R² represents analkanediyl or an alkenediyl group which optionally contains at thebeginning (or end) or within the hydrocarbon chain an oxygen atom, asulphur atom, an SO₂ group, an NH group, an N-alkyl group, a carbonylgroup and/or a thiocarbonyl group, and

Z represents in each case optionally substituted monocyclic or bicyclic,saturated or unsaturated heterocyclyl, heterocyclylamino orheterocyclylimino.

The novel substituted aromatic thiocarboxamides of the general formula(I) are obtained if substituted aromatic nitrites of the general formula(II)

in which

R¹, R², R³ and Z have the meanings given above are reacted with hydrogensulphide (H₂S) or with thioacetamide, optionally in the presence of areaction auxiliary and optionally in the presence of a diluent.

The novel substituted aromatic thiocarboxamides of the general formula(I) are notable for strong and selective herbicidal activity.

In the definitions, the saturated or unsaturated hydrocarbon chains,such as alkyl, alkanediyl, alkenyl or alkinyl—alone or in conjunctionwith heteroatoms, such as in alkoxy, alkylthio or alkylamino—are eachstraight-chain or branched.

Halogen generally represents fluorine, chlorine, bromine or iodine,preferably fluorine, chlorine or bromine, especially fluorine orchlorine.

The invention preferably relates to compounds of the formula (I) inwhich

R¹ represents hydrogen, fluorine, chlorine or bromine,

R² represents the following group

—A¹—A²—A³

 in which

A¹ represents a single bond, or represents oxygen, sulphur, —SO—, —SO₂—,—CO— or the group —N—A⁴—, in which A⁴ represents hydrogen, hydroxyl,C₁-C₄-alkyl, C₃-C₄-alkenyl, C₃-C₄-alkinyl, C₁-C₄-alkoxy, phenyl,C₃-C₄-alkylsulphonyl or phenylsulphonyl,

A¹ additionally represents in each case optionally fluorine- orchlorine-substituted C₁-C₆-alkanediyl, C₂-C₆-alkenediyl,C₂-C₆-alkinediyl, C₃-C₆-cycloalkanediyl, C₃-C₆-cycloalkenediyl orphenylene,

A² represents a single bond, or represents oxygen, sulphur, —SO—, —SO₂—,—CO— or the group —N—A⁴—, in which A⁴ represents hydrogen, hydroxyl,C₁-C₄-alkyl, C₃-C₄-alkenyl, C₃-C₄-alkinyl, C₁-C₄-alkoxy, phenyl,C₁-C₄-alkylsulphonyl or phenylsulphonyl,

A² additionally represents in each case optionally fluorine- orchlorine-substituted C₁-C₆-alkanediyl, C₂-C₆-alkenediyl,C₂-C₆-alkinediyl, C₃-C₆-cycloalkanediyl, C₃-C₆-cycloalkenediyl orphenylene,

A³ represents hydrogen, hydroxyl, amino, cyano, isocyano, thiocyanato,nitro, carboxyl, carbamoyl, thiocarbamoyl, sulpho, chlorosulphonyl,halogen, or represents in each case optionally halogen- orC₁-C₄-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl,alkylsulphonyl, alkylamino, dialkylamino, alkoxycarbonyl ordialkoxy(thio)phosphoryl having in each case 1 to 6 carbon atoms in thealkyl groups, or represents in each case optionally halogen-substitutedalkenyl, alkenyloxy, alkenylamino, alkylideneamino, alkenyloxycarbonyl,alkinyl, alkinyloxy, alkinylamino or alkinyloxycarbonyl having in eachcase 2 to 6 carbon atoms in the alkenyl, alkylidene or alkinyl groups,or represents in each case optionally halogen-, cyano-, carboxyl-,C₁-C₄-alkyl- and/or C₁-C₄-alkoxy-carbonyl-substituted cycloalkyl,cycloalkyloxy, cycloalkylalkyl, cycloalkylalkoxy, cycloalkylideneamino,cycloalkyloxycarbonyl or cycloalkylalkoxycarbonyl having in each case 3to 6 carbon atoms in the cycloalkyl groups and optionally 1 to 4 carbonatoms in the alkyl groups, or represents in each case optionally nitro-,cyano-, carboxyl-, halogen-, C₁-C₄-alkyl-, C₁-C₄-halogenoalkyl-,C₁-C₄-alkyloxy-, C₁-C₄-halogenoalkyloxy- and/orC₁-C₄-alkoxy-carbonyl-substituted phenyl, phenyloxy, phenyl-C₁-C₄-alkyl,phenyl-C₁-C₄-alkoxy, phenyloxycarbonyl or phenyl-C₁-C₄-alkoxycarbonyl,(in each case optionally totally or partially hydrogenated) pyrrolyl,pyrazolyl, iridazolyl, triazolyl, fliryl, thienyl, oxazolyl, isoxazolyl,thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl,pyrimidinyl, triazinyl, pyrazolyl-C₁-C₄-alkyl, furyl-C₁-C₄-alkyl,thienyl-C₁-C₄-alkyl, oxazolyl-C₁-C₄-alkyl, isoxazole-C₁-C₄-alkyl,thiazole-C₁-C₄-alkyl, pyridinyl-C₁-C₄-alkyl, pyrimidinyl-C₁-C₄-alkyl,pyrazolylmethoxy or furylmethoxy, or represents perhydropyranylmethoxyor pyridylmethoxy,

R³ represents hydrogen, fluorine, chlorine or bromine or together withR² represents an alkanediyl or alkenediyl group having in each case upto 4 carbon atoms which optionally contains at the beginning (or end) orwithin the hydrocarbon chain an oxygen atom, a sulphur atom, an SO₂group, an NH group, an N—C₁-C₄-alkyl group, a carbonyl group and/or athiocarbonyl group, and

Z represents in each case monocyclic or bicyclic, saturated orunsaturated hetero-cyclyl, heterocyclylamino or heterocyclylimino havingin each case 2 to 6 carbon atoms and 1 to 4 nitrogen atoms in theheterocyclic ring system, which optionally additionally contains anoxygen atom or sulphur atom and/or optionally up to three groups fromthe series —CO—, —CS—, —SO— and/or SO₂—, and which is optionallysubstituted by one or more groups from the series nitro, hydroxyl,amino, cyano, carboxyl, carbainoyl, thiocarbamoyl, halogen, C₁-C₆-alkyl(which is optionally substituted by halogen or C₁-C₄-alkoxy),C₂-C₆-alkenyl or C₂-C₆-alkinyl (which are in each case optionallysubstituted by halogen), C₁-C₆-alkoxy or C₁-C₆-alkoxy-carbonyl (whichare in each case optionally substituted by halogen or C₁-C₄-alkoxy),C₂-C₆-alkenyloxy or C₂-C₆-alkinyloxy (which are in each case optionallysubstituted by halogen), C₁-C₆-alkylthio, C₂-C₆-alkenylthio orC₂-C₆-alkinylthio (which are in each case optionally substituted byhalogen), C₁-C₆-alkylamino or di-(C₁-C₄-alkyl)-amino, C₃-C₆-cycloalkylor C₃-C₆-cycloalkyl-C₁-C₄-alkyl (which are in each case optionallysubstituted by halogen and/or C₁-C₄-alkyl), phenyl, phenoxy, phenylthio,phenylsulphinyl, phenylsulphonyl or phenylamino (which are in each caseoptionally substituted by nitro, cyano, halogen, C₁-C₄-alkyl,C₁-C₄-halogenoalkyl, C₁-C₄-alkyloxy, C₁-C₄-halogenoalkyloxy and/orC₁-C₄-alkoxy-carbonyl).

The invention particularly relates to compounds of the fonnula (I) inwhich

R¹ represents hydrogen, fluorine or chlorine,

R² represents the following group

—A¹—A²—A³

 which

A¹ represents a single bond, or represents oxygen, sulphur, —SO—, —SO₂—,—CO— or the group —N—A⁴—, in which A⁴ represents hydrogen, hydroxyl,methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy,methylsulphonyl or ethylsulphonyl,

A² additionally represents methylene, ethane-1,1-diyl, ethane-1,2-diyl,propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl,propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl orpropine-1,3-diyl,

A² represents a single bond, or represents oxygen, sulphur, —SO—, —SO₂—,—CO— or the group —N—A⁴—, in which A⁴ represents hydrogen, hydroxyl,methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy,methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl orphenylsulphonyl,

A² additionally represents methylene, ethane-1,1-diyl, ethane-1,2-diyl,propane-1,1-diyl, propane-1,2-diyl, propane-1,3-diyl, ethene-1,2-diyl,propene-1,2-diyl, propene-1,3-diyl, ethine-1,2-diyl, propine-1,2-diyl orpropine-1,3-diyl,

A³ represents hydrogen, hydroxyl, amino, cyano, nitro, carboxyl,carbamoyl, sulpho, fluorine, chlorine, bromine, or represents in eachcase optionally fluorine-, chlorine-, methoxy- or ethoxy-substitutedmethyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- ort-pentyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, n-,i-, s- or t-pentyloxy, methylthio, ethyl;-thio, n- or i-propylthio, n-,i-, s- or t-butylthio, methylsulphinyl, ethyl-sulphinyl, n- ori-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- ori-propylsulphonyl, methylamino, ethylamino, n- or i-propylamino, n-, i-,s-or t-butylamino, dimethylamino, diethylamino, methoxycarbonyl,ethoxycarbonyl, n- or i-propoxycarbonyl, dimethoxyphosphoryl,diethoxyphosphoryl, dipropoxyphosphoryl or diisopropoxyphosphoryl, orrepresents in each case optionally fluorine- or chlorine-substitutedpropenyl, butenyl, propenyloxy, butenyloxy, propenylamino, butenylamino,propylideneamino, butylideneamino, propenyloxycarbonyl,butenyloxycarbonyl, propinyl, butinyl, propinyloxy, butinyloxy,propinylamino, butinylamino, propinyloxycarbonyl or butinyloxycarbonyl,or represents in each case optionally fluorine-, chlorine-, cyano-,carboxyl-, methyl-, ethyl-, n- or i-propyl-, methoxycarbonyl- orethoxycarbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cyclopropyl-oxy, cyclobutyloxy, cyclopentyloxy,cyclohexyloxy, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl,cyclohexylmethyl, cyclopropyl-methoxy, cyclobutylmethoxy,cyclopentylmethoxy, cyclohexylmethoxy, cyclopentylideneamino,cyclohexylideneamino, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl,cyciopentylmethoxycarbonyl or cyclohexyl-methoxycarbonyl, or representsin each case optionally nitro-, cyano-, carboxyl-, fluorine-, chlorine-,bromine-, methyl-, ethyl-, n- or i-propyl-, trifluoromethyl-, methoxy-,ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-,methoxycarbonyl- and/or ethoxycarbonyl-substituted phenyl, phenyloxy,benzyl, phenylethyl, benzyloxy, phenyloxycarbonyl, benzyloxycarbonyl,(in each case optionally completely or partially hydrogenated) pyrrolyl,pyrazolyl, imidazolyl, triazolyl, iuryl, thienyl, oxazolyl, isoxazolyl,thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl,pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl,oxazolylmethyl, isoxazolemethyl, thiazolmethyl, pyridinylmethyl,pyrimidinylmethyl, pyrazolylmethoxy, finylmethoxy or pyridylmethoxy,

R³ represents hydrogen, fluorine or chlorine or together with R²represents an alkanediyl or alkenediyl group having in each case 1 to 3carbon atoms which optionally contains at the beginning (or end) orwithin the hydrocarbon chain an oxygen atom, a sulphur atom, an NHgroup, an N-methyl group, a carbonyl group and/or a thiocarbonyl group,and

Z represents in each case monocyclic or bicyclic, saturated orunsaturated heterocyclyl, heterocyclylamino or heterocyclylimino havingin each case 2 to 5 carbon atoms and 1 to 3 nitrogen atoms in theheterocyclic ring system, which optionally additionally contains anoxygen atom or sulphur atom and/or optionally up to two groups from theseries —CO—, —CS—, —SO— and/or SO₂—, and which is optionally substitutedby one or more groups from the series nitro, hydroxyl, amino, cyano,carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine; methyl,ethyl, n- or i-propyl, n-, i-, s- or t-butyl, (which are optionallysubstituted by fluorine, chlorine, methoxy or ethoxy); propenyl,butenyl, propinyl or butinyl (which are in each case optionallysubstituted by fluorine or chlorine); methoxy, ethoxy, n- or i-propoxy,n-, i-, s- or t-butoxy, methoxy-carbonyl or ethoxycarbonyl (which are ineach case optionally substituted by fluorine, chlorine, methoxy orethoxy); propenyloxy, butenyloxy, propinyloxy or butinyloxy (which areoptionally substituted by fluorine or chlorine); methyl-thio, ethylthio,n- or i-propylthio, n-, i-, s- or t-butylthio, propenylthio,butenyl-thio, propinylthio or butinylthio (which are in each caseoptionally substituted by fluorine or chlorine); methylamino,ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino,dimethylamino or diethylamino; cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl orcyclohexylmethyl (which are in each case optionally substituted byfluorine, chlorine, methyl, ethyl, n- or i-propyl), phenyl, phenoxy,phenylthio, phenylsulphinyl, phenylsulphonyl, or phenylamino (which arein each case optionally substituted by nitro, cyano, fluorine, chlorine,bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy,ethoxy, n- or i-propoxy, difluoro-methoxyi trifluoromethoxy,methoxycarbonyl or ethoxycarbonyl).

Very particularly preferred groups of compounds of the formula (I) arethe compounds of the formulae (Ia), (Ib) and (Ic) drawn below

where

R¹, R² and Z have the meanings indicated above as particularlypreferred,

R⁴ and R⁵ are identical or different and independently of one another ineach case individually represent hydrogen, fluorine, chlorine, methyl orethyl— or in the formula (Ib) can also together represent oxygen orsulphur— and

Q represents oxygen, sulphur, N-methyl or N-ethyl.

Z in the general formulae (I) and ((Ia), (Ib) and (Ic) represents inparticular the heterocyclic groups listed below

 where in each case

Q¹ represents a group from the series —CO—, —CS—, —CH₂—, —CH(OH)—,—CHCl—, —CHBr—, —C(═CH₂)—, —C(═CHF)—, —C(═CF₂)—, —C(═CHCl)—, —C(═CHBr)—,—C(═CHOCHF₂)—, —C(═CHOCF₃)—, —C(═CHOCH₂CF₃)—,

Q² represents oxygen, sulphur or a group from the series —CO—, —CS—,—CH₂—, —CHF—, —CF₂—, —CHCl—, —CHBr—, —CHOCHF₂—, —CHOCF₃—, —CHOCH₂CF₃—,

R⁶ represents hydrogen, amino, nitro, cyano, carboxyl, carbarnoyl,fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, cyclopropyl,difluoromethyl, trifluoromethyl, chlorodifluoromethyl, methoxy, ethoxy,n- or i-propoxy, difluoromethoxy, trifluoromethoxy,chlorodifluoromethoxy, methylthio, ethylthio, n- or i-propylthio,difluoromethylthio, trifluoromethylthio, chloro-difluoromethylthio,methylamino, ethylamino, n- or i-propylamino, dimethylamino,diethylamino, methoxycarbonyl or ethoxycarbonyl, and

R⁷ represents hydrogen, hydroxyl, amino, cyano, methyl, ethyl, n- ori-propyl, difluoromethyl, methoxy, ethoxy, n- or i-propoxy,

or where optionally two adjacent groups—R⁶ and R⁶ or R⁷ and R⁶ or R⁶ andR⁷— together represent in each case optionally fluorine-, chlorine-,bromine-, methyl-, ethyl-, n- or i-propyl-substituted alkanediyl oralkenediyl having in each case up to 4 carbon atoms which is optionallyinterrupted by oxygen, sulphur or a group from the series —SO—, SO₂—,—N(CH₃)— or N(C₂H₅)— at the beginning (or at the end) or within thehydrocarbon chain.

The definitions of radicals listed above, indicated in general or inranges of preference, apply both to the end products of the formula (I)and, correspondingly, to the respective starting materials andintermediates required for preparation. These radical definitions can becombined as desired with one another, which therefore includes anydesired combinations between the indicated ranges of preferredcompounds.

Examples of the compounds of the formnula (I) according to the inventionare listed in the groups below.

In this formula, R¹, R² and R³ have the meanings indicated in thefollowing list:

Synthesis Ex. No. R¹ R² R³ 1 H F H 2 H Cl H 3 H Cl Cl 4 Cl F H 5 F F H 6F F Cl 7 F CH₃ H 8 F C₂H₅ H 9 F —CH₂Cl H 10 F F F 11 F —NHC₂H₅ H 12 F—CH₂CN H 13 F —N(CH₃)SO₂C₂H₅ H 14 Cl —N(CH₃)SO₂C₂H₅ H 15 Cl—N(CH₃)SO₂C₂H₅ Cl 16 F —NH—COCF₃ H 17 F —OH H 18 Cl —OH H 19 F —CH(CH₃)₂H 20 F —NH—SO₂—CH₃ H 21 F —SO₂—CH₃ H 22 F —SO₂—O—CH₃ H 23 F —SO₂—NH—CH₃H 24 F —COOCH₃ H 25 F —CO—NH—CH₃ H 26 Cl —COOCH₃ Cl 27 Cl —COOC₂H₅ H 28F —O—C₂H₅ H 29 F —N(C₂H₅)SO₂C₂H₅ H 30 F —N(SO₂CH₃)₂ H 31 F —CO—N(CH₃)₂ H32 F —S—CH₂—C≡CH H 33 Cl —S—CH₂—C≡CH F 34 F —S—CH₂—C≡CH Cl 35 F—O—CH(CH₃)—C≡CH H 36 F —S—CH₂—COOCH₃ H 37 F —O—CH₂CH₂—OCH₃ H 38 F—O(CH₂CH₂O)₂CH₃ H 39 F —O—CH₂—CH═CH₂ H 40 F —O—CH₂—C≡CH H 41 F —SH H 42F —S—CH₃ H 43 F —S—C₂H₅ H 44 F —S—CH(CH₃)₂ H 45 F —O—CH₂—CF₃ H 46 F—O—CH(CH₂F)₂ H 47 F

H 48 F

H 49 F —NH—SO₂C₂H₅ H 50 Cl —NH—SO₂C₂H₅ H 51 F —NH—SO₂C₂H₅ Cl 52 F—NH—SO₂CH(CH₃)₂ H 53 F —NH—SO₂C₄H₉ H 54 F —N═CH—OC₂H₅ H 55 F—N═C(CH₃)OC₂H₄ H 56 F —N═C(OCH₃)₂ H 57 F —N═CH—N(CH₃)₂ H 58 F —SCN H 59F —SO₂Cl H 60 F —O—CS—N(CH₃)₂ H 61 F —S—CO—N(CH₃)₂ H 62 F—NH—P(O)(CH₃)OC₂H₅ H 63 F —NH—P(O)(OC₂H₅)₂ H 64 F —NH—COC₂H₅ H 65 F—N(CH₃)COCF₃ H 66 F —NH—COCH(CH₃)₂ H 67 F —NH—CO—CO—C(CH₃)₃ H 68 F—NH—CO—NH₂ H 69 F —NH—CO—NHCH₃ H 70 F —NH—CO—N(CH₃)₂ H 71 F —N(COCH₃)₂ H72 F —NH—COCH(CH₃)Cl H 73 F —S—CH₂—CH═CH₂ H 74 Cl —S—CH₂—CH═CH₂ H 75 F—S—CH(CH₃)C≡CH H 76 F —S—CH(CH₃)COOC₂H₅ H 77 F —S(O)—CH₃ H 78 F

H 79 F

H 80 F

H 81 F

H 82 F

H 83 F

H 84 F —O—CH₂—CN H 85 F —O—SO₂—CH₃ H 86 F —OCH₂—CH(Cl)═CH₂ H 87 F—O—CH₂—COOCH₃ H 88 F —O—CHF₂ H 89 F —OCOOCH₂CH₂Cl H 90 F—OCH₂P(O)(OC₂H₅)₂ H 91 Cl —O—CH(CH₃)P(O)(OC₂H₅)₂ H 92 F

H 93 F

H 94 F —O—N(C₂H₅)₂ H 95 F

H 96 F

H 97 F

Cl 98 Cl

H 99 F

F 100 F

H 101 F

H 102 F

H 103 F —NCH(CH₃)₂SO₂C₂H₅ H 104 F —N(CH₃)SO₂CH(CH₃)₂ H 105 H—N(CH₃)SO₂C₂H₅ Cl 106 Cl —N(CH₃)SO₂C₄H₉ H 107 F —N(CH₃)SO₂C₂H₅ H 108 F—N(CH₃)SO₂CH₃ H 109 F —N(SO₂C₂H₅)₂ H 110 F —N(SO₂CH₃)SO₂C₂H₅ H 111 F

H 112 F —N(CH₃)₂ H 113 F —NH₂ H 114 Cl —NH₂ H 115 Cl —O—CH(CH₃)₂ H 116 F—O—CH(CH₃)₂ H 117 F

H 118 Cl

H 119 F —O—CH₂—COOC₂H₅ H 120 F —S—CH₂—COOCH₃ H 121 F —S—CH₂—COOC₂H₅ H122 Cl —S—CH₂—COOC₂H₅ H 123 F —CH₂—CH(Cl)COOCH₃ H 124 F—CH₂—CH(Cl)COOC₂H₅ H 125 F —CH₂—CH(Cl)CONHC₂H₅ H 126 Cl—CH₂—CH(Cl)CONHC₂H₅ H 127 Cl

H 128 F

H 129 F —COOC₃H₇-i H

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In In this formula, R¹, R² and R³ have, for example, meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formnula, R¹, R² and R³ have, for example, the meaningsindicated above in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R ² and R³ have, for example, the meaningsindicated above in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this fonnula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R² and R³ have, for example, the meanings indicatedabove in Group 1.

In this formula, R¹, R⁴ and R⁵ have, the meanings indicated in thefollowing list:

Ex. No. R¹ R⁴ R⁵ 1 F CH₃ CH₃ 2 Cl CH₃ CH₃ 3 H CH₃ CH₃ 4 F Cl CH₃ 5 F ClCl 6 F C₂H₅ CH₃

In this formula, R¹, R⁴ and R⁵ have, for example, the meanings indicatedabove in Group 85.

In this formula, R¹, R⁴ and R⁵ have, for example, the meanings indicatedabove in Group 85.

In this formula, R¹, R⁴ and R⁵ have, for example, the meanings indicatedabove in Group 85.

In this formula, R¹, R⁴ and R⁵ have, for example, the meanings indicatedabove in Group 85.

Using, for example,2-(2-fluoro-4-cyano-5-methoxy-phenyl)-4-methyl-5-difluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-oneand hydrogen sulphide as starting materials, the course of reaction ofthe process according to the invention can be illustrated by thefollowing equation:

A general definition of the substituted aromatic nitriles to be used asstarting materials in the process according to the invention for thepreparation of the compounds of the general formula (I) is given by theformula (II). In the formula (II), R¹, R², R³ and Z preferably or inparticular have those meanings which have already been indicated above,in connection with the description of the compounds of the formula (I),as preferred or, respectively, as particularly preferred for R¹, R², R³and Z.

The starting materials of the formula (II) are known and/or can beprepared by known processes (cf. EP-A 370332; DE-A 4238125; DE-A4303376; U.S. Pat. No. 5084084; Preparation Examples).

Suitable diluents for carrying out the process according to theinvention are the customary organic solvents. These include, inparticular, aliphatic, alicyclic or aromatic, optionally halogenatedhydrocarbons, for example benzine, benzene, toluene, xylene,chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane,dichloromethane, chloroform, tetrachloromethane; ethers, such as diethylether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycoldimethyl or diethyl ether; ketones, such as acetone, butanone or methylisobutyl ketone; nitrites, such as acetonitrile, propionitrile orbenzonitrile; amides, such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone orhexamethyl-phosphoric triamide; esters, such as methyl acetate or ethylacetate, sulphoxides, such as dimethyl sulphoxide, azines, such aspyridine, alcohols, such as methanol, ethanol, n- or i-propanol,ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,mixtures thereof with water, or pure water.

The process according to the invention is preferably carried out in thepresence of a suitable reaction auxiliary. Suitable such auxiliaries areall customary inorganic or organic bases. These include, for example,alkaline earth metal or alkali metal hydrides, hydroxides, amides,alcoholates, acetates, carbonates or hydrogen carbonates, for examplesodium hydride, sodium amide, sodium methylate, sodium ethylate,potassium tert-butylate, sodium hydroxide, potassium hydroxide, ammoniumhydroxide, sodium acetate, potassium acetate, calcium acetate, ammoniumacetate, sodium carbonate, potassium carbonate, potassium hydrogencarbonate, sodium hydrogen carbonate or ammonium carbonate and alsobasic organic nitrogen compounds, such as trimethylamine, triethylamine,tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine,N,N-dimethylaminopyridine, diazabicyclooctane (DABCO),diaza-bicyclononene (DBN) or diazabicycloundecene (DBU).

The reaction temperatures when carrying out the process according to theinvention can be varied within a relatively large range. It is generallycarried out at temperatures between 0° C. and 100° C., preferably attemperatures between 10° C. and 80° C.

The process according to the invention is generally carried out underatmospheric pressure. However, it is also possible to operate underelevated or reduced pressure, generally between 0.1 bar and 10 bar.

To carry out the process according to the invention the startingmaterials of the formula (II) are introduced, generally in a suitablediluent in the presence of a reaction auxiliary, and the hydrogenslulphide or the thioacetamide is slowly metered in. The hydrogensulphide or the thioacetamide are preferably employed in a relativelylarge excess. The reaction mixture is stirred for a number of hours atthe particular temperature required. Working up in the process accordingto the invention is effected in each case in accordance with customarymethods (cf. the Preparation Examples).

The active compounds according to the invention can be used asdefoliants, desiccants, haulm killers and, especially, as weedkillers.By weeds, in the broadest sense, there are to be understood all plantswhich grow in locations where they are not wanted. Whether thesubstances according to the invention act as total or selectiveherbicides depends essentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Matricaria, Anthernis, Galinsoga, Chenopodium, Urtica, Senecio,Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala,Lindemia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.

Dicotyledon crops of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleura, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena,Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

Depending on the concentration, the compounds are suitable for totalweed control, for example on industrial terrain and rail tracks, and onpaths and areas with or without tree stands. Equally, the compounds canbe employed for controlling weeds in perennial crops, for exampleforests, ornamental tree plantings, orchards, vineyards, citrus groves,nut orchards, banana plantations, coffee plantations, tea plantations,rubber plantations, oil palm plantations, cocoa plantations, soft fruitplantings and hopfields, in lawns, turf and pastures, and for selectiveweed control in annual crops.

The compounds of the formula (I) according to the invention areparticularly suitable for selective control of monocotyledon anddicotyledon weeds in monocotyledon and dicotyledon crops, both pre- andpost-emergence.

To a certain extent, the compounds of the formula (I) also show afungicidal action, for example against Pyricularia oryzae in rice.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusts, pastes, soluble powders, granules, suspoemulsion concentrates,natural and synthetic materials impregnated with active compound, andmicroencapsulations in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surfactants, that isemulsifiers and/or dispersants and/or foam-formers.

If water is used as an extender, organic solvents can, for example, alsobe used as auxiliary solvents. Liquid solvents which are mainly suitableare: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinatedaromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons such ascyclohexane or paraffins, for example petroleum fractions, mineral andvegetable oils, alcohols such as butanol or glycol as well as theirethers and esters, ketones such as acetone, methyl ethyl ketone, methylisobutyl ketone or cyclohexanone, strongly polar solvents such asdimethylformamide and dimethyl sulphoxide, and water.

Suitable solid carriers are:

for example ammonium salts and ground natural minerals such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and ground synthetic minerals such as highly disperse silica,alumina and silicates; suitable solid carriers for granules are: forexample crushed and fractionated natural rocks such as calcite, marble,pumice, sepiolite and dolomite, or else synthetic granules of inorganicand organic meals, and granules of organic material such as sawdust,coconut shells, maize cobs and tobacco stalks; suitable emulsifiersand/or foam-formers are: for example non-ionic and anionic emulsifiers,such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates and protein hydrolysates; suitabledispersants are: for example lignin-sulphite waste liquors andmethylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latexes such as gum arabic,polyvinyl alcohol and polyvinyl acetate, or else natural phospholipidssuch as cephalins and lecithins, and synthetic phospholipids can be usedin the formulations. Further additives can be mineral and vegetableoils.

It is possible to use colourants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyes such asalizarin dyes, axo dyes and metal phthalocyanine dyes, and tracenutrients such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

The formulations generally comprise between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

For controlling weeds, the active compounds according to the invention,as such or in the form of their formulations, can also be used asmixtures with known herbicides, finished formulations or tank mixesbeing possible.

Possible components for the mixtures are known herbicides, examplesbeing anilides, for example, diflufenican and propanil; arylcarboxylicacids, for example dichloropicolinic acid, dicamba and picloram;aryloxyalkanoic acids, for example 2,4 D, 2,4 DB, 2,4 DP, fluroxypyr,MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters, for examplediclofop(-methyl), fenoxaprop(-ethyl), fluazifop(-butyl), haloxyfop(-methyl) and quizalofop(-ethyl); azinones, for example chloridazon andnorflurazon; carabamates, for example chlorpropham, desmedipham,phenmaedipham and propham; chloroacetanilides, for example alachlor,acetochlor, butachlor, metazachlor, metolachlor, pretilachlor andpropachlor; dinitroanilines, for example oryzalin, pendimethalin andtrifluralin; diphenyl ethers, for example acifluorfen, bifenox,chlornethoxynil (X-52), chlornitrofen, fluoroglycofen, fomesafen,halosafen, lactofen, nitrofen and oxyfluorfen; ureas, for examplechlortoluron, cumyluron (JC-940), diuron, dymron (daimuron),fluormeturon, isoproturon, linuron and methabenzthiazuron;hyroxylamines, for example alloxydim, clethodim, cycloxydim, sethoxydimand tralkoxydim; imidazolinones, for example imazethapyr,imazamethabenz, imazapyr and imazaquin; nitriles, for examplebromoxynil, dichlobenil and ioxynil; oxyacetamides, for examplemefenacet; sulphonylureas, for example AC-014 (AC-322140),amidosulfuron, bensulfuron(-methyl), chlorimuron(-ethyl), chlorsulfuron,cinosulfuron, DPX47, HOE-404, imazosulfuiron, metsulfuron(-methyl),nicosulfuron, primisulfuron, pyrazosulfuron(-ethyl),thifensulfuiron(-methyl), triasulfuron and tribenuron(-methyl);thiocarbamates, for example butylate, cycloate, diallate, dimepiperate,EPTC, esprocarb, molinate, prosulphocarb, thiobencarb (benthiocarb) andtriallate; triazines, for example atrazine, cyanazine, dimethametryn,prometryne, simazin, simetryne, terbutryne and terbutylazin;triazinones, for example hexazinon, metamitron and metribuzin; others,for example aminotriazole, benfuresate, bensulide, bentazone,benzofenap, bromobutide, butamifos, cafenstrole (CH-900), cinmethylin,clomazone, clomeprop, clopyralid, DEH-112, difenzoquat, dimethenamid,dithiopyr, ethofumesate, flumetsulam, fluorochloridone, glufosinate,glyphosate, amiprophos(-methyl), anilofos, etobenzanid (HW-52),isoxaben, KPP-314, KUH-833, KUH-911, KUH-920, MK-243, naproanilide,NSK-850, oxadiazon, piperophos, propanil, pyrazolate, pyrazoxyfen,pyributicarb, pyridate, quinchlorac, quinmerac, sulphosate andtridiphane.

Mixtures with other known active compounds, such as fuingicides,insecticides, acaricides, nematicides, bird repellants, plant nutrientsand soil conditioners, are also possible.

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are used in the customary manner, for example bywatering, spraying, atomizing or spreading.

The active compounds according to the invention can be applied eitherbefore or after emergence of the plants. They can also be incorporatedinto the soil before sowing.

The amount of active compound used can vary within a substantial range.It depends essentially on the nature of the desired effect. In general,the amounts used are between 10 g and 10 kg of active compound perhectare of soil surface, preferably between 50 g and 5 kg per ha.

The preparation and use of the active compounds according to theinvention can be seen from the examples which follow.

PREPARATION EXAMPLES EXAMPLE 1

Hydrogen sulphide is passed at from 50° C. to 60° C. to saturation pointinto a mixture of 5.5 g (15 mmol) of2-(4-cyano-2-fluoro-5-ethylsulphonylamino-phenyl)-5,6,7,8-tetrahydro-1,2,4-triazolo[4,3-a]pyridin-3(2H)-one,5 ml of triethylamine and 50 ml of pyridine and the mixture is stirredat 60° C. for 30 minutes more. It is then concentrated in vacuo, theresidue is stirred with 2 N hydrochloric acid and the solids arefiltered off. The solid product is recrystallized from isopropanol.

4.8 g (80% of theory) of2-(2-fluoro-5-ethylsulphonylamino4-thiocarbamoyl-phenyl)-5,6,7,8-tetrahydro-1,2,4-triazolo[4,3-a]pyridin-3(2H)-oneare obtained of melting poin 220° C.

EXAMPLE 2

4.04 g (0.04 mol) of triethylamine are added to 6.3 g (0.02 mol) of2-(2-fluoro-4-cyano-5-amino-phenyl)4-ethyl-5-trifluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-onein 100 ml of acetone. Hydrogen sulphide is passed in rapidly at 23° C.,and the internal temperature rises to 33° C. The reaction is completeafter 1 hour. The solution is concentrated on a rotary evaporator andthe residue is recrystallized from isopropanol.

2.9 g (42% of theory) of2-(2-fluoro4-thiocarbamoyl-5-amino-phenyl)4-ethyl-5-trifluoromethyl-2,4-dihydro-3H-1,2,4-triazol-3-oneare obtained of melting point 161° C.

EXAMPLE 3

11 g (0.0276 mol) of2-(2-fluoro-4-cyano-5-ethylsulphonylaminophenyl)-4-methyl-5-difluoromethyl-2,4-dihydro-3H-1,2,4-triazole-3-thioneare stirred at 70° C. for 4.5 hours in 100 ml of pyridine while passingin hydrogen sulphide. The solution is concentrated on a rotaryevaporator, the residue is stirred in water, the mixture is acidifiedwith concentrated hydrochloric acid, and precipitated product isfiltered off, washed with water and recrystallized from isopropanol.

9 g (77% of theory) of2-(2-fluoro4-thiocarbamoyl-5-ethylsulphonylaminophenyl)4-methyl-5-difluoromethyl-2,4-dihydro-3H-1,2,4-triazole-3-thioneare obtained of melting point 183° C.

In analogy to Preparation Examples 1, 2 and 3 and in accordance with thegeneral description of the preparation process according to theinvention it is also possible, for example, to prepare the compounds ofthe formula (I) listed in Table 1 below.

TABLE 1 Examples of the compounds of the formula (I) Melting Ex. No. R¹R² R³ Z point (° C.)  4 F F H

110  5 F —NH—SO₂—C₂H₅ H

143  6 F

H

162  7 F —NH—SO₂—C₂H₅ H

237 (Triethyl- ammonium salt)  8 F F H

220  9 F —NH—SO₂—C₂H₅ H

218 10 F —NH—SO₂—C₂H₅ H

185 11 F F H

218 12 F —OC₂H₅ H

202 13 F —NH—SO₂—C₂H₅ H

210 14 F —NH—SO₂—C₂H₅ H

203 15 F F H

185 16 F

H

170 17 F —OCH(CH₃)₂ H

206 18 F OH H

250 19 F

H

 98 20 F —NH—SO₂—C₂H₅ H

208 21 F —NH—SO₂—C₂H₅ H

 55 22 F —NH—SO₂—C₂H₅ H

(amorphous) 23 F —NH—SO₂—C₂H₅ H

183 24 F

H

167 25 F —NH—SO₂—CH₃ H

130 26 F —NH—SO₂—CH₃ H

243 27 F F H

199 28 F —NH—SO₂—C₂H₅ H

202 29 F —NH—SO₂—CH₃ H

200 30 F —NH—SO₂—CH(CH₃)₂ H

204 31 F —NH—SO₂—C₂H₅ H

195 32 F

H

122 33 F —O—CH₂—C≡CH H

190 34 F —NH—SO₂—CH₃ H

178 35 F —NH—SO₂—C₃H₇ H

203 36 F —NH—SO₂—C₂H₅ H

199 37 F —NH—SO₂—C₂H₅ H

153 38 F —NH—SO₂—C₂H₅ H

206 39 F —NH—SO₂—C₂H₅ H

167 40 F F H

130 41 F —OCH₂CF₃ H

173 42 F —OC₂H₄OCH₃ H

148 43 F —OC₂H₅ H

155 44 F —OC₃H₇ H

130 45 F F H

131 46 F —OCH(CH₃)₂ H

202 47 F —OC₂H₅ H

185 48 F —NH—SO₂—C₂H₅ H

111 49 H —NH—SO₂—C₂H₅ H

118 50 F —NH—SO₂—C₃H₇-n H

143 51 F —OC₂H₄OC₂H₄OCH₃ H

168 52 F —NH—SO₂—C₃H₇-n H

(amorphous) 53 F —NH—SO₂—C₃H₇-n H

232 54 F —NH—SO₂—C₃H₇-i H

226 55 F —NH—SO₂—C₃H₇-i H

187 56 F —NH—SO₂C₃H₇-i H

236 57 F —NH—SO₂C₃H₇-i H

252 58 F —NH—SO₂C₃H₇-i H

109 59 F —NH—SO₂C₃H₇-i H

207 60 F —NH—SO₂C₃H₇-i H

215 61 F —N(CH₃)—SO₂C₂H₅ H

102 62 F —NH—SO₂—C₂H₅ H

185 63 Cl —NH—SO₂—C₂H₅ H

121 64 F F H

157 65 F —NH—SO₂—C₂H₅ H

195 66 F —OH H

193 (decomp) DBU salt

Preparation of the Starting Compounds EXAMPLE II-1

5.8 g (0.042 mol) of potassium carbonate are added at room temperatureto 6.3 g (0.034 mol) of 4-methyl-3-trifluoromethyl-1,2,4-triazolin-5-one(cf. e.g. U.S. Pat. No. 3,780,052) and 5.4 g (0.034 mol) of2,4,5-trifluorobenzonitrile (cf. e.g. EP 191181) in 150 ml of dimethylsulphoxide and the mixture is subsequently heated at 100° C. for 14hours. For working up, the cooled reaction mixture is placed in water,adjusted to a pH of 2 with dilute hydrochloric acid and subjectedseveral times to extraction with dichloromethane. The combined organicphases are dried over sodium sulphate and concentrated in vacuo. Theresidue is chromatographed over silica gel (eluent: dichloromethane).

6.2 g (60% of theory) of1-(4-cyano-2,5-difluorophenyl)-4-methyl-3-trifluoromethyl-1,2,4-triazolin-5-oneare obtained of melting point 74° C.

EXAMPLE II-2

0.83 g (0.006 mol) of potassium carbonate is added at room temperatureto 1.52 g (0.005 mol) of1-(4-cyano-2,5-difluorophenyl)4-methyl-3-trifluoromethyl-1,2,4-triazolin-5-oneand 0.48 g (0.005 mol) of methanesulphonamide in 50 ml of dimethylsulphoxide and the mixture is subsequently heated at 120° C. for 12hours. For working up, the cooled reaction mixture is placed in water,adjusted to a pH of 2 with dilute hydrochloric acid and subjectedseveral times to extraction with dichloromethane. The combined organicphases are dried over sodium sulphate and concentrated in vacuo. Theresidue is chromatographed over silica gel (eluent:dichloromethane/methanol 20:1).

0.55 g (28% of theory) of1-(4-cyano-2-fluoro-5-methylsulphonylaminophenyl)4-methyl-3-trifluoromethyl-1,2,4-triazolin-5-oneis obtained of melting point 67° C.

EXAMPLE II-3

0.3 g (10 mmol) of sodium hydride (80%) is added at from 0° C. to 5° C.to an initial charge of 1.8 g (10 mmol) of ethyl3-amino-4,4,4-trifluoro-crotonate in 30 ml of dimethylformamide and 2 mlof toluene. The mixture is stirred at from 0° C. to 5° C. for 30minutes. After the mixture has been cooled to −70° C., 0.9 g (5 mmol) of4-cyano 2,5-difluoro-phenyl isocyanate—dissolved in 10 ml of toluene—isadded and the mixture is stirred at from −60° C. to −70° C. for 150minutes. After the cooling bath has been removed, 2 ml of acetic acidare added. The mixture is then diluted with water to about twice thevolume and subjected to extraction with ethyl acetate. The organic phaseis concentrated and the residue is crystallized with diisopropyl ether.

1.1 g (69% of theory) of1-(4-cyano-2,5-difluoro-phenyl)-3,6dihydro-2,6-dioxo-4-trifluoromethyl-1-(2H)-pyrimidineare obtained of melting point 194° C.

EXAMPLE II-4

A mixture of 0.83 g (3 mmol) of1-(4-cyano-2,5-difluorophenyl)-3,6-dihydro-2,6-dioxo3,4-dimethyl-1(2H)-pyrimidine, 0.32 g (3 mmol) of methane sulphonamide,0.6 g of potassium carbonate and 10 m of dimethyl sulphoxide is heatedat 120° C. for 10 hours. After cooling, the mixture is poured intoice-water and acidfied with 2 N hydrochloric acid. It is then subjectedto extraction with ethyl acetate and organic phase is washed with water,dried with sodium sulphate and filtered. The solvent is carefullyremoved from the filtrate by distillation under a water-pump vacuum.

0.8 g (76% of theory) of1-(4-cyano-2-fluoro-5-methylsulphonylaminophenyl)-3,6-dihydro-2,6-dioxo-3,4-dimethyl-1(2H)-pyrimidineis obtained as crystalline residue (melting point >250° C.).

USE EXAMPLES Example A

Pre-emergence Test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours,watered with the preparation of active compound. It is expedient to keepconstant the amount of water per unit area. The concentration of theactive compound in the preparation is of no importance, only the amountof active compound applied per unit area being decisive. After threeweeks, the degree of damage to the plants is rated in % damage incomparison to the development of the untreated control. The figuresdenote:

0%=no action (like untreated control)

100%=total destruction

TABLE A Pre-emergence test/greenhouse Active compound Applica-(Synthesis tion Example rate Amaran- Cheno- Matri- Portu- Sola- Number)(g/ha) Barley Maize thus podium caria laca num (3) 125 0 0 100 100 100 100 100 (5) 125 0 0 100 100 90  90 100 (6) 125 0 30  100 100 95 100 100(7) 125 30  0 100 100 95 100  95

TABLE B Pre-emergence test/greenhouse Active compound Applica-(Synthesis tion Example rate Abu- Amaran- Cheno- Matri- Portu- Sola-Number) (g/ha) Wheat Maize thilon thus podium caria laca num 19 60 10 0100 95 100 100 100 100 20 60 20 0 100 100 100 100 100 100 21 60 0 0 100100 100 100 100 100 22 250 0 20 100 100 100 100 95 100 23 60 0 0 95 7095 100 95 70 24 30 0 20 100 95 100 100 100 100 25 30 0 0 100 100 90 100100 100 26 60 0 0 100 80 100 100 100 90 4 250 0 10 80 50 70 95 90 70 5125 0 0 10 100 100 70 90 100 3 60 0 0 100 100 100 100 100 100 6 60 20 30100 100 100 100 100 95 7 125 50 0 95 100 100 95 100 95 8 60 40 0 100 100100 95 95 100 9 60 0 0 100 100 100 95 90 100 1 125 0 0 100 100 100 95100 100 12 60 20 0 70 70 100 95 95 70 13 60 0 0 100 100 100 70 90 100 1660 10 0 95 20 100 90 80 80 17 30 0 0 100 100 100 100 100 100 28 60 0 20100 100 100 100 100 100 29 60 0 0 100 100 100 100 100 100 30 60 0 0 100100 100 90 100 100 31 60 0 0 100 100 100 100 100 100 32 30 10 0 — 100100 100 95 100 33 30 10 10 95 95 100 100 100 100 34 60 0 0 100 100 100100 100 100 35 60 0 0 100 100 100 90 95 100 40 250 20 0 30 40 100 95 10080 41 60 20 30 100 100 100 100 100 100 45 125 0 0 95 100 100 100 90 9546 60 0 70 100 100 100 100 100 100 47 30 0 0 100 95 100 100 100 100 4860 0 0 100 100 100 100 100 100 51 30 0 20 100 — 100 95 100 100

Example B

Post-emergence Test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with thepreparation of active compound in such a way as to apply the particularamounts of active compound desired per unit area. After three weeks, thedegree of damage to the plants is rated in % damage in comparison to thedevelopment of the untreated control.

The figures denote:

0%=no action (like untreated control)

100%=total destruction

TABLE C Post-emergence test/greenhouse Active compound Applica-(Synthesis tion Example rate Abu- Amaran- Cheno- Sola- Vero- Number)(g/ha) Wheat Maize thilon thus podium num nica 19 4 5 20 95 95 95 100100 20 4 0 15 100 95 95 100 95 21 4 5 60 90 100 70 100 100 22 30 15 0100 100 40 100 20 23 30 0 50 95 — 90 100 100 24 30 15 70 100 100 100 100100 25 15 0 50 100 100 100 100 100 26 15 0 30 50 90 50 50 100 5 15 10 20100 100 100 100 100 3 30 10 30 100 100 100 100 100 6 8 30 50 100 100 100100 95 7 60 10 50 100 100 95 100 95 8 60 10 30 100 100 100 100 100 9 6010 30 100 100 100 100 100 1 15 10 50 100 95 95 100 100 12 8 10 30 100100 95 100 100 13 15 0 30 95 100 80 100 90 16 60 20 60 95 100 100 100100 17 8 10 10 100 100 95 100 100 28 30 0 30 100 100 90 100 100 29 8 5 070 100 90 100 95 30 8 0 50 100 100 95 100 70 31 8 0 70 100 100 90 100100 32 4 15 30 100 100 95 100 100 33 4 20 60 100 100 100 100 100 34 15 030 100 100 100 100 100 35 30 0 25 100 100 90 100 95 40 125 10 5 50 70100 100 90 41 15 20 50 100 80 90 100 95 43 15 0 50 100 95 100 100 100 448 0 15 100 100 100 95 100 45 8 10 40 95 95 95 100 — 46 8 15 20 100 10095 100 100 47 8 10 10 100 100 95 100 100 48 8 5 60 100 100 80 100 100 498 0 60 60 100 10 100 100 50 15 5 70 100 95 80 100 95 51 15 15 60 100 10070 100 100

What is claimed is:
 1. A substituted aromatic thiocarboxamide compoundof the formula:

wherein, R¹ is chlorine or fluorine; R₂ is NHSO₂CH₃, NHSO₂CH(CH₃)₂, orNHSO₂C₂H₅; and Z is


2. The compound of claim 1, wherein R¹ is fluorine; R₂ is NHSO₂C₂H₅; and


3. The compound of claim 1, wherein R¹ is fluorine; R₂ is NHSO₂C₂H₅; and


4. The compound of claim 1, wherein R¹ is fluorine; R² is NHSO₂C₂H₅; and


5. The compound of claim 1, wherein R¹ is fluorine; R₂ is NHSO₂CH₃; and


6. The compound of claim 1, wherein R¹ is fluorine; R₂ is NHSO₂CH(CH₃)₂;and


7. The compound of claim 1, wherein R¹ is chlorine; R₂ is NHSO₂C₂H₅; and


8. An herbicidal composition comprising at least one substitutedaromatic thiocarboxamide compound of any one of claims 1-7 and anextender.
 9. A method of combatting unwanted plants comprising applyingan herbicially effective amount of a substituted aromaticthiocarboxamide compound of any one of claims 1-7 to said unwantedplants or to an area in which it is desired to exclude said unwantedplants.
 10. A process for the preparation of the substituted aromaticthiocarboxamide compound of claim 1, wherein substituted aromaticnitriles of the formula:

in which R¹, R₂ and Z are as defined in claim 1, are reacted withhydrogen sulfide or with thioacetamide, optionally in the presence of areaction auxiliary and optionally in the presence of a diluent.